Phosphanes, their method of production and use in metal complexes

ABSTRACT

A process for the preparation of the formula 
     
       
         Ar 1   3−x P[(Ar 2 (OZ) y ] x   I 
       
     
     wherein Ar 1  and Ar 2  are individually aromatic of 6 to 20 carbon atoms or heteroaromatic of 4 to 9 carbon atoms, each unsubstituted or substituted with at least one member of the group consisting of halogen, carboxyl, —OH, alkyl of 1 to 6 carbon atoms, phenyl and naphthyl, Ar 1  has one valence and R 2  has y+1 valences, x is an integer of 1, 2 or 3, y is 1 or 2, Z is carbohydrate with a glycosidic bond comprising reacting a hydrocarbon halide of the formula 
     
       
         Z′—X  II 
       
     
     
       
         when Z′ has the definition of Z with —OH protected and X is chlorine, bromine or fluorine with a phosphane of the formula 
       
     
     
       
         Ar 1   3−x P[(Ar 2  (OH) y ] x   III 
       
     
     in a multi-phase reaction medium in the presence of a base and a phase transfer catalyst to form a phosphane of the formula 
     
       
         Ar 1   3−x P[(Ar 2 (OZ 1 ) y ] x   IV 
       
     
     and removal of the protective groups to form a compound of Formula I, metal complexes thereof and various processes.

FIELD OF THE INVENTION

The invention relates to hydrophilic phosphanes, a process for theirproduction, their use in metal complexes, these metal complexes andtheir use in catalytic conversions.

STATE OF THE ART

Many chemical conversions of organic compounds are carried out underconditions of homogeneous catalysis. A general problem of homogeneouscatalysis is the simple and economical separation, following theconversion, of the catalyst system from the organic products. Thecatalysts should advantageously be simple to separate from the organicproducts and be recyclable into the conversion process. A solution tothese problems represents the so-called two-phase catalysis in which thecatalyst system and the organic products are present in different phasesand can be separated one from the other by simple decanting. Such twophase-catalyzed conversions are described for example in W. A. Herrmann,C. W. Kohlpaintner, Angew. Chem. 1993, 105, 1588-1609 and in P. Kalck,F. Monteil, Adv. Organomet. Chem. 1992, 34, 219. In these conversions ahydrophilic aqueous phase is frequently used as the catalyst phase,however, it is also possible to use fluoridated hydrocarbons orpolyethylene glycols. The prerequisite for an effective two-phasecatalysis is high solubility of the catalyst system in the catalystphase and low solubility in the product phase. For this purpose mainlyhydrophilically modified ligands have been used in the past when usingmetal complex catalysts. A typical example of this are sulfonatedtriaryl phosphanes such as are described for example in W. A. Herrmann,C. W. Kohlpaintner, Angew. Chem. 1993, 105, 1588-1609 and in P. Kalck,F. Monteil, Adv. Organomet. Chem. 1992, 34, 219. They are usedcommercially for the hydroformylation of propene. Up to now ionic groupssuch as —SO₃ ⁻, —CO₂ ⁻, —NR₃ ⁺, —P(O)O₂ ²⁻ have substantially been usedto increase the hydrophilicity of phosphane ligands. This is describedfor example in M. Beller, B. Cornils, C. D. Frohning, C. W.Kohlpaintner, J. Mol. Catal. 1995, 104, 17-85. Ionic functionalities canbe of disadvantage in various processes due to the salt concentrationspresent. Furthermore, no chiral ionic groups are accessible. To avoidthese disadvantages, neutral substituents can be used. As neutralsubstituents in order to increase the hydrophilicity of phosphanes havepreviously been used for example polyethylene glycol groups. This isdescribed for example in B. Cornils, Angew. Chem. 1995, 107, 1709-1711.

OBJECTS OF THE INVENTION

The task of the present invention is providing hydrophilic phosphanecompounds which can be used as metal complex ligands for the productionof catalysts and which make accessible a multiplicity of structuralvariants including chiral centers.

SUMMARY OF THE INVENTION

This task is solved through a process for the production of phosphaneshaving the general formula (I)

Ar¹ _(3−x)P(Ar²(OZ)_(y))_(x)  (I)

in which Ar¹ and Ar² independently are aromatic C₆₋₂₀ radicals orheteroaromatic C₄₋₉ radicals substituted, if appropriate, by halogenatoms, carboxyl groups, hydroxyl groups, C₁₋₆ alkyl groups, phenylgroups or naphthyl groups wherein Ar¹ has one and Ar² has y+1 freevalences,

Z is a carbohydrate radical with a glycosidic bond,

x has the value 1, 2 or 3, and

y has the value 1 or 2, by

(1) the conversion of carbohydrate halogenoses having the generalformula (II)

Z′—X  (II)

 in which Z′ is a radical Z as specified above, in which the hydroxylgroups are substituted by protective groups, and X represents Br, Cl orF,

with a phosphane having the general formula (III)

Ar¹ _(3−x),P(Ar²(OH)_(y))_(x)  (III)

 in which Ar¹, Ar², x and y have the above meaning

in a multiphase reaction medium in the presence of a base and of a phasetransfer catalyst,

into a phosphane having the general formula (IV)

Ar¹ _(3−x)P(Ar²(OZ′)_(y))_(x)  (IV)

 in which Ar¹, Ar², x, y and Z′ have the above specified meaning, and

(2) removal of the protective groups from Z′.

It was found according to the invention that the compounds having thegeneral formulas (I) and (IV) are accessible through the phasetransfer-catalyzed conversion of carbohydrate halogenoses.

Only O. Neunhoeffer, L. Lamza, Chem. Ber. 1961, 94, 2514-2521 havepublished the synthesis of a triphenyl phosphane in which one phenylradical in the p-position is substituted by a glucosyl radical, in whichthe hydroxyl groups are protected by acetyl groups. The production takesplace through the glycosylation in aqueous acetone with potassiumhydroxide as a base. The yield was 8% and was thus substantially lessthan the yields obtainable in the process according to the invention.

The phosphanes produced according to the invention have the generalformula (I)

Ar¹ _(3−x)P(Ar²(OZ)_(y))_(x)  (I)

In the formula (I) the radicals Ar¹ and Ar² are aromatic C₆₋₂₀ radicalsor heteroaromatic C₄₋₉ radicals. As aromatic radicals they are thereinpreferably independently phenyl, naphthyl, biphenyl or binaphthylradicals. If several Ar¹ or Ar² radicals are present, each individualradical can independently be one of the above radicals. At least onearomatic radical Ar¹ or Ar² is therein preferably a phenyl radical and,especially preferred, two of the aromatic radicals are phenyl radicals.In particular all of the aromatic radicals Ar¹ and Ar² are phenylradicals.

The radicals Ar¹ and/or Ar² as the heteroaromatic radicals comprisepreferably 1 or 2, especially preferably 1 hetero atom selected fromoxygen, sulphur and nitrogen. Especially preferred are radicals based onpyridine, furan or thiophene. The aromatic radicals can, if appropriate,be substituted independently of one another, for example by halogenatoms, carboxyl groups, hydroxyl groups, C₁₋₆, preferably C₁₋₂ alkylgroups, phenyl groups or naphthyl groups. These substituents can bepresent in addition to the substituent(s) OZ of the radical Ar². Thesubstituents are preferably hydroxyl groups, in particular maximally onehydroxyl group per benzene nucleus is present.

Ar¹ comprises one and Ar² comprises y+1 free valences. y has therein thevalue 1 or 2. If the radical Ar² is a radical based on a phenyl radical,at y=1 the free valences can be present in the o-, m- or p-position. Thefree valences are preferably present in the o- or p-, in particular inthe p-position. In the case of biphenyl radicals or binaphthyl radicalsas the radicals Ar², the valences are preferably present in differentbenzene nuclei i.e. each phenyl or naphthyl radical preferably containsat least one of the free valences. y has preferably the value 1.

x can have the value 1, 2 or 3. x preferably has the value 1 or 2, inparticular the value 1. y has preferably the value 1.

Preferred compounds of formula (I) are such in which y=1 and x=1 or 2.The radical Ar¹ is therein preferably a phenyl radical or a phenylradical substituted by an hydroxyl in the p-position. The radical Ar² ispreferably a p-phenylene radical or a binaphthyl radical, in particulara 1,1′-binaphthyl radical in which the free valences are in the2,2′-position.

The radical Z is a carbohydrate radical with a glycosidic bond which isderived from a sugar radical. Z is preferably derived from glucose,mannose, galactose, fructose, cellobiose, saccharose, glucosamine,N-acetylglucosamine or their stereoisomers. Consequently, Z ispreferably derived from a glycosidically linked 5 or 6-membercarbohydrate. Corresponding amines or N-acetylamines of these compoundscan also be used. Each radical Z independently has one of the abovemeanings.

Z is preferably derived from glucose, galactose or N-acetylglucosamine.

The phosphanes according to the invention having the general formula (I)are produced by the conversion of carbohydrate halogenoses having thegeneral formula (II)

Z′—X  (II)

Z′ is therein a radical Z as was described above, with the differencethat the hydroxyl groups are substituted by protective groups. Suitableprotective groups which protect the hydroxyl groups during theconversion against reacting are known to a person skilled in the art.Examples are acetyl, benzoyl, benzyl or allyl groups. The protectivegroups are distinguished thereby that they prevent in particular areaction of the protected hydroxyl groups in glycosylation reactions.Acetyl protective groups are preferably used. The production of thecompounds Z′—X can take place for example according to the processdescribed in R. R. Schmidt, Angew. Chem. 1986, 98, 213-236. Thecorresponding monosacharide is therein converted for example with a baseand an acylation agent and, if appropriate, an acylation catalyst. Theresulting peracylated compound is converted into glacial acetic acidwith an HX acid, preferably hydrobromic acid. Following standardprocessing methods, the protected halogenose is obtained. The compoundshaving the formula Z′—X in which X is bromine, chlorine, fluorine, inparticular bromine or chlorine, are converted with a phosphane havingthe general formula (III)

Ar¹ _(3−x)P(Ar²(OH)_(y))_(x)  (III)

Ar¹, Ar², x, y have therein the above specified meaning. The conversiontakes place in a multiphase, in particular two-phase, reaction medium inthe presence of a base and of a phase transfer catalyst. The reactiontakes place at conversion temperatures of 0 to 80° C., preferably 10 to60° C., in particular 20 to 50° C. As the reaction media can be used allsuitable two- or multiphase reaction media. One phase of the reactionmedium is preferably an aqueous phase, and in this phase water can bepresent in a mixture with a watersoluble organic solvent. The secondphase is an organic phase which is only slightly or not at all mixablewith water. Examples of suitable two-phase reaction media aredichloromethane/water, acetone/water, toluene/water, toluene/ethyleneglycol, tert. butyl methylether/water or dichloromethane/polyethyleneglycol.

Suitable bases are alkali and alkaline earth hydroxides, basic aminesand salts of weak acids. Basic amines are for example pyridine,tributylamine, benzylamine, triethylamine, diisopropylethylamine. Saltsof weak acids are for example sodium acetate, potassium benzoate, sodiumcarbonate, sodium hydrogenphosphate. Alkali and alkaline earthhydroxides, such as NaOH, KOH, LiOH, Ca(OH)₂, Mg(OH)₂ are preferablyused, with NaOH and KOH being especially preferred.

Catalysts suitable as phase transfer catalysts are for example describedin Eckehard N. Dehmlow, Sigrid S. Dehmlow, Phase Transfer Catalysis, 3rdEdition, VCH, Weinheim, New York, Basel, Cambridge, Tokio (1993).Tetra-n-C₁₋₁₂ alkylammonium salts are preferably used. Especiallypreferred is therein the use of tetra-n-butyl ammonium salts. Ascounterions can be used all suitable inorganic counterions, for examplehalogenides or hydrogen sulfates. Especially preferred examples aretetra-n-butyl ammonium bromide, tetra-n-butyl ammonium hydrogen sulfate,tetra-n-butyl ammonium chloride, tetra-n-butyl ammonium nitrate. Thephase transfer catalysts are preferably used in quantities from 1 to 90percent by weight relative to halogenose.

To prepare N-acetylglucosamine compounds the following steps arepreferably carried out:

Suitable N-acetylglucosamine donors are described for example in T.Mukaiyama et al., Chem. Lett. 1984, 907; K. Higashai, Chem. Pharm. Bull.1990. 38, 3280. Of the various glucosamine donors the glucopyranosylchloride is accessible directly in one stage by conversion with acetylchloride. This is described for example in D. Horton, Org. Synth., Coll.Vol. V, 1973, 1. Furthermore, the process described in G. Chittenden,Carbohydr. Res. 1993, 242, 297 can be followed. As phase transfercatalyst for the coupling reaction is preferably used zinc chloridewhich yields good alpha/beta selectivity (T. Norberg, J. Carbohydr.Chem. 1990, 9, 721). The conversion takes preferably place in thepresence of co-catalysts. Suitable co-catalysts are described forexample in R. Bittman, Tetrahedron Lett., 1994, 35, 505. Instead of thetrityl chloride used in this paper, a 4,4′-dimethoxytrityl halogenide isused in combination with zinc fluoride. This permitted preventingepimerization, moreover, the conversion occurs more readily. When usingthis catalyst combination a marked shortening of the reaction time couldbe attained even with relatively large reaction mixtures. Thus for thepreparation of N-acetylglucosamine derivatives the catalyst combinationzinc chloride/4,4′-dimethoxy trityl halogenide is preferably used asphase transfer catalyst. Moreover, when using this catalyst system thechromatographic purification of the products is simplified. The shorterreaction time permits the specific synthesis of beta-glycosidicallylinked

N-acetyl glucosamine derivatives with good yields and withoutepimerization occurring.

After the conversion into phosphanes having the general formula (IV),the protective groups are removed from Z′. Suitable processes aredescribed for example in R. R. Schmidt, Angew. Chem. 1986, 98, 213-236.The splitting of acetyl protective groups takes preferably place underbasic conditions.

The process according to the invention makes possible the production ofa multiplicity of carbohydrate-substituted triphenyl phosphanes in shortreaction times and with high yield.

The invention also relates to phosphanes having the general formula (I),such as are defined above. The invention furthermore relates tophosphanes having the general formula (IV) such as are defined above.The exception are compounds in which Ar¹ =phenyl, Ar² =p-phenylene,Z′=acetyl-protected glucosyl radical, x=1, y=1.

Examples of preferred compounds having the general formula (IV) are thefollowing:diphenyl-(o-hydroxyphenyl)-phosphine-2,3,4,6-tetra-O-acetyl-,β-D-glucopyranoside,1-O-[4-(diphenylphosphino)phenyl]-2-acetamido-2-desoxy-3,4,6-O-acetyl-β-D-glucopyranoside.

Preferred phosphanes having the general formula (I) correspond to thesecompounds with the protective groups having been removed.

The phosphanes according to the invention having the general formula (I)can be used for the production of metal complexes. As the central metalatom the following metals can be used therein: Ru, Pd, Rh, Ni, Pt, Co,Ir, Cu, Fe, Mn. In addition to the phosphanes according to the inventionhaving the general formula (I), the metal complexes can comprise asligands further ligands, such as halogen atoms, hydrogen atoms, carbonmonoxide, etc.

The invention also relates to ruthenium complexes having the generalformula (V)

RuH₂(CO)L₃  (V)

in which L is a phosphane having the general formula (I) such as isdescribed above. The complexes are produced by converting the phosphanewith ruthenium(III) chloride trihydrate according to the processdescribed in J. J. Levison, S. D. Robinson, J. Chem. Soc. A 1970,2947-2954.

The invention also relates to palladium complexes having the generalformula (VI)

L₂PdX₂  (VI)

in which L is a phosphane having the general formula (I) as describedabove and X is Cl, Br, I, preferably Cl, or acetate. The productiontakes place for example with lithium tetrachloropalladate(II) in ethanolaccording to the process described in G. Brauer, Handbuch derpraparativen anorganischen Chemie, Ferdinand Enkel Verlag, 1981, Vol. 3,p. 2014.

The complexes in which X is acetate, can be generated in situ fromPd(OAc)₂ and the corresponding ligands in the reaction mixture. Theratio of Pd to ligand is therein preferably 1:1 to 1:20, especiallypreferred 1:2 to 1:10, in particular approximately 1:3. Under reducingconditions are therefrom formed palladium complexes having the generalformula (VII)

 L_(z)Pd  (VII)

in which L is a phosphane having the general formula (I) and z has thevalue 3 or 4.

The catalysts according to the invention can be used in catalytic C—Ccoupling reactions. Examples of such coupling reactions are the Heckreaction, the Suzuki reaction or hydroformylations, they are furthermoresuitable for hydrogenations of unsaturated compounds, hydrogenations ofaromatic nitro substances, allyl substitutions, carbonylations andpolymerizations.

In the following the invention will be explained in further detail inconjunction with examples.

EXAMPLE 1

1-O-[4-(diphenylphosphino)phenyl]-2-acetamido-2-desoxy-β-D-glucopyranoside(glycosylation)

202 mg (0.726 mmol) (p-hydroxyphenyl)diphenylphospane and 125 mg (0.368mmol) tetra-n-butylammonium hydrogen sulfate are dissolved in 2 mlmethylene chloride and mixed with 2 ml 1 M sodium hydroxide solution.133 mg (0.364 mmol)2-acetamido-3,4,6-tri-O-acetyl-2-desoxy-α-D-glucopyranosyl chloride (1)and after 5 minutes an additional 133 mg (0.364 mmol) of 1 are added.After 15 minutes 0.5 ml 1 M sodium hydroxide solution and 267 mg (0.730mmol) of 1 and lastly, after 70 minutes, 0.5 ml 1 M sodium hydroxidesolution and 259 mg (0.708 mmol) of 1 are added. After 1.5 hours thereaction mixture is diluted with 30 ml ethyl acetate. The organic phaseis washed twice, each time with 20 ml 1 M sodium hydroxide solution,twice with 20 ml water each time and once with 15 ml saturated sodiumchloride solution. The mixture is dried over magnesium sulfate and thesolvents are removed by distillation. The residue is taken up in 10 mlabsolute methanol and under nitrogen mixed with 0.5 ml of a 1 Mmethanolic sodium methanolate solution. After agitating the solution atambient temperature, it is diluted with 10 ml methanol and neutralizedwith Amberlyst H 15 (strongly acidic cation exchanger). The ionexchanger is separated by filtration and the solvent is removed bydistillation. The residue is chromatographed withchloroform/methanol/hexane 6:1:1 (v/v/v) over 55 g silica gel 60. Yield:238 mg (68% with respect to phosphane).

1-O-[4-(diphenylphosphino)phenyl]-2-acetamido-2-desoxy-β-D-glucopyranoside(Protection removal)

0.33 mmol1-O-[4-(diphenylphosphino)phenyl]-2-acetamido-2-desoxy-3,4,6-O-acetyl-β-D-glucopyranosideare suspended in 25 ml methanol and a solution of 2 mg sodium in 25 mlmethanol is added. After approximately 2 hours of agitation at ambienttemperature, a solution is formed. It is neutralized with acidic ionexchanger (Amberlyst H 15), filtered and the residue is concentrated todryness. The residue is washed with water and recrystallized fromethanol/water. Yield: 0.32 mmol (96%).

EXAMPLE 2

Diphenyl-(p-hydroxyphenyl)-phosphine-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside

To a solution of diphenyl-(p-hydroxyphenyl)-phosphine (778 mg, 2.80mmol) in water/acetone (10 ml/6ml) is added potassium hydroxide (0.35g). While stirring the mixture, a solution of acetobromoglucose (2.63 g,6.4 mmol) in acetone (15 ml) is added dropwise. The mixture is agitatedfor 2 days at ambient temperature. After removing the solvent in arotary evaporator the residue is rinsed several times with water. Theremaining residue is recrystallized from ethanol. The glucopyranoside isobained in the form of a slightly yellow solid substance (450 mg,26.4%).

R_(f)-value (toluene/ethyl acetate 1/1): 0.61; NMR-¹H (300 MHz, DMSO):7.45-7.18 (m 12 H); 7.07-7.01 (m, 2H), 5.62 (d, J=8,0 Hz, 1H); 5.40 (m,J=8.8 Hz, 1H), 5.06 (m, J=9.7 Hz, J=8.2 Hz, 1H); 5.00 (m, J=9.7 Hz, 1H);4.28-4.04 (m, 3H (4s, each 3H).

Diphenyl-(p-hydroxyphenyl)-phosphine-β-D-glucopyranoside

Diphenyl-(p-hydroxyphenyl)-phosphine-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside(196 mg, 0.32 mmol) is dissolved in absolute methanol (5 ml) and mixedwith 30% sodium methanolate solution (0.5 ml). The solution is agitatedfor 3 hours at ambient temperature and neutralized with acidic ionexchanger (Dowex 50 W×8). After removal of the solvent, theglucopyranoside is obtained as a slightly yellow solid substance (139mg, 97%).

R_(f)-value (dichloromethane/methanol 10/1): 0.3.

EXAMPLE 3

Diphenyl-(o-hydroxyphenyl)-phosphine-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside

To a solution of diphenyl-(o-hydroxyphenyl)-phosphine (4.33 g, 15.6mmol) in water/acetone (60 ml/35 ml) is added potassium hydroxide (1.91g). While stirring the mixture a solution of acetobromoglucose (14.25 g)in acetone (15 ml) is added dropwise. The mixture is agitated for 2 daysat ambient temperature. After removing the solvent in a rotaryevaporator, the residue is rinsed several times with water. Theremaining residue is recrystallized from ethanol. The glucopyranoside isobtained as a slightly yellow solid substance (1.84 g, 19.4%)

R_(f)-value (toluene/ethyl acetate 1/1): 0.6; NMR-¹H (300 MHz, DMSO):7.50-7.00 (m 14H); 5.62 (d, J=8.1 Hz 1H); 5.42 (m, 1=8.7 Hz, 1H), 5.10(m, J=9.7 Hz, J=8.1 Hz, 1H); 5.00 (m, J=9.7 Hz, 1H); 4.28-4.06 (m, 3H);2.03-1.95 (4s each 3H).

Diphenyl-(o-hydroxyphenyl)-phosphine-β-D-glucopyranoside

Diphenyl-(o-hydroxyphenyl)-phosphine-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside(450 mg, 0.74 mmol) is dissolved in absolute methanol (5 ml) and mixedwith 30% sodium methanolate solution 0.5 ml). The solution is agitatedfor 3 hours at ambient temperature and neutralized with acidic ionexchanger (Dowex 50 W×8). After removing the solvent the glucopyranosideis obtained in the form of a slightly yellow solid substance (312 mg,96%).

R_(f)-value (dichloromethane/methanol 10/1): 0.4.

EXAMPLE 4

Preparation of GlcNAc Chloride

To 500 ml acetyl chloride are added over a period of 2 minutes 250 g(1.13 mol) N-acetyl-(D)-glucosamine. The mixture is stirred for 19 hoursat ambient temperature. After adding methylene chloride (500 ml) thesolution is placed onto a mixture of ice/water (500 ml) and the organicphase is rapidly separated. The organic phase is rapidly washed withsaturated sodium hydrogen carbonate solution, dried over magnesiumsulfate and filtered. The mixture is concentrated to one half of thevolume in a rotary evaporator. While rapidly agitating the mixture, 500ml diethylether are added. After 12 hours the resulting precipitate isaspirated and dried under reduced pressure. The chloride is obtained inthe form of a slightly brown powder (269 g, 62%).

Diphenyl-(o-hydroxyphenyl)-phosphine-N-acetyl-2-amino-2-desoxy-3,4,6-tri-O-acetyl-β-D-glucopyranoside

To a suspension of zinc(II) chloride (139 mg, 1.03 mmol) and4,4′-dimethoxy tritylchloride (122 mg, 1.34 mmol) in dry dichloromethane(15 ml) the chloride (1.3 eq, 497 mg, 1.34 mmol) anddiphenyl-(o-hydroxyphenyl)-phosphine (287 mg, 1.34 mmol) are added. Themixture is agitated for 13 hours at ambient temperature (DC controlmethylene chloride/methanol 50/1). After adding methylene chloride, themixture is washed with sat. sodium hydrogen carbonate solution. Afterremoving the solvent in a rotary evaporator, the residue is purified bycolumn chromatography (methylene chloride/methanol 100/1-40/1). Theyield of the glycoside obtained is 37% (232 mg).

R_(f)-value (dichloromethane/methanol 50/1): 0.4; NMR-¹H (300 MHz,DMSO): 7.51-7.01 (m, 14H); 5.60 (d, J=8.2 Hz, 1H); 5.40 (m, J=8.6 Hz,1H), 5.15 (m, J=9.7 Hz, J=8.2 Hz, 1H); 5.03 (m, J=9.6 Hz, 1H); 4.28-4.02(m, 3H); 2.17-1.95 (4s each 3H).

Catalytic Conversions EXAMPLE 5

Suzuki Reaction

4-bromacetophenone or 1-bromo-4-chlorobenzene were converted accoding tothe Suzuki reaction with phenylboric acid (H₅C₆—B(OH)₂ to thecorrespondingly substituted biphenylenes. In the reaction the bromineatom was substituted by the phenyl radical. A mixture of 15 mmolphenylboric acid, 13.5 mmol 4-bromaceto phenone or1-bromo-4-chlorobenzene, 40.5 mmol Na₂CO₃ 10 H₂O, 0.01 mol percent,relative to phenyl boric acid, Pd(OAc)₂, and ligand L at a molar ratioPd:L of 1:3 were heated to a temperature of 60° C. in a solvent mixturecomprising 9 ml ethanol, 9 ml water and 18 ml di-n-butyl ether or 12 mlethanol, 6 ml water and 15 ml toluene while stirring the mixture. Themixture was subsequently heated for 2 hours to a temperature of 78° C.The conversion product was isolated and the yield was determined. As theligand was used:1-O-[4-(diphenylphosphino)phenyl]-2-acetamido-2-desoxy-β-D-glucopyranoside(3a). For purposes of comparison the trisodium salt of 3,3′,3″-phosphanetriylbenzene-sulfonic acid (TPPTS) was used. The results of theconversion are listed in Table 1 for the conversion with4-bromacetophenone.

TABLE 1 Experiment Ligand Yield [%] Solvent TON 1 3a 87 1 8700 2 TPPTS*67 1 6700 3 3b 90 2 9000 4 TPPTS* 87 2 8700 *TPPTS = trisodium salt of3,3′,3″-phosphane triylbenzene-sulfonic acid, comparison ligand

Solvent 1: 9 ml ethanol, 9 ml water, 18 ml di-n-butyl ether

Solvent 2: 12 ml ethanol, 6 ml water, 15 ml toluene

TON: version number=mol (product)/mol (catalyst)

Results of the conversion with 1-bromo-4-chlorobenzene are listed inTable 2.

TABLE 2 Experiment Ligand Yield [%] Solvent TON 5 3a 56 1 5600 6 TPPTS*40 1 4000 7 3b 71 2 7100 8 TPPTS* 44 2 4400

The results listed in Table 1 and 2 demonstrate that yields andconversions with catalyst which comprise the ligands according to theinvention are significantly higher than when using the comparison ligandTPPTS.

EXAMPLE 5

Heck Reaction

In the Heck reaction, carried out as a two-phase reaction,4-bromacetophenone or 1-bromo-4-nitrobenzene, respectively, wasconverted with styrene to form the correspondingly substitutedstilbenes. In the process a mixture comprising 15 mmol4-bromacetophenone or 1-bromo-4-nitrobenzene, 22.5 mmol (1.5equivalents) styrene, 16.5 mmol (1.1 equivalents) NaOAc 3 H₂O, Pd(OAc)₂in the quantities specified in Table 3 and the ligands listed in theTable at a ratio of Pd:L=1:3 in a mixture comprising 10 ml xylene and 10ml ethylene glycol was allowed to react under agitation at 130° C. for20 hours. The conversion product was isolated and its yield wasdetermined. The results are summarized in Table 3 and 4 below:

TABLE 3 Heck reaction with 4-bromacetophenone Experiment Ligand Yield[%] (EZ) Catalyst mol [%] TON  9 3a 98 (89:11) 1 98 10 3b 80 (95:5)  180 11 TPPTS* 79 (92:8)  1 79

TABLE 4 Heck reaction with 1-bromo-4-nitrobenzene Experiment LigandYield [%] (EZ) Catalyst mol [%] TON 12 3a 85 (95:5) 0.1 850 13 3b 88(95:5) 0.1 880 14 TPPTS* 78 (94:6) 1  78

Reference is made to the explanations regarding Table 1. The catalystswith the lingands according to the invention exhibit high yields andhigh conversion numbers at a good ratio of E to Z isomers.

What is claimed is:
 1. A process for the preparation of the phosphanesof formula Ar¹ _(3−x)P[Ar²(OZ)_(y]) _(x)  I wherein Ar¹ and Ar² areindividually aromatic rings, each having 6 to 20 carbon atoms, orheteroaromatic rings, each having 4 to 9 carbon atoms, eachunsubstituted or substituted with at least one member of the groupconsisting of halogen, carboxyl, —OH, alkyl of 1 to 6 carbon atoms,phenyl and naphthyl, Ar¹ has one valence and R² has y+1 valences, x isan integer of 1, 2 or 3, y is 1 or 2, Z is a residue of a carbohydrateselected from the group consisting of glucose, mannose, galactose,fructose, cellobiose, saccharose, glucosamine, and their stereoisomers,and their N-acetylamine derivatives, said process comprising forming onenew glycosidic bond for each substituent bound to the phosphane byreacting a hydrocarbon halide of the formula Z′—X  II  wherein Z′ hasthe definition of Z with any —OH protected and X is chlorine, bromine orfluorine, with a phosphane of the formula Ar¹_(3−x)P[Ar²(OH)_(y)]_(x)  III  in a reaction medium, which contains atleast two immiscible liquid phases, at 0° to 80° C. in the presence of abase and a phase transfer catalyst to form a phosphane of the formulaAr¹ _(3−x)P[Ar²(OZ¹)_(y)]_(x)  IV  and removing the protective groups toform the compound of Formula
 1. 2. A phosphane of the formula Ar¹_(3−x)P[Ar²(OZ)_(y)]_(x)  I wherein Ar¹ and Ar² are individuallyaromatic rings, each having 6 to 20 carbon atoms, or heteroaromaticrings, each having 4 to 9 carbon atoms, each unsubstituted orsubstituted with at least one member of the group consisting of halogen,carboxyl, —OH, alkyl of 1 to 6 carbon atoms, phenyl and naphthyl, Ar¹has one valence and R² has y+1 valences, x is an integer of 1, 2 or 3, yis 1 or 2, Z is a carbohydrate, selected from the group consisting ofglucose, mannose, galactose, fructose, cellobiose, saccharose,glucosamine, and their stereoisomers, and their N-acetylaminederivatives with the proviso that when x and y are 1, Ar¹ is not phenyl,Ar² is not p-phenylene and Z is not β-glucosyl.
 3. The process of claim1 wherein Z is derived from glucose, galactose, or n-acetyl glucosamine.4. The process of claim 1 wherein Ar¹ and Ar² are individually selectedfrom the group consisting of phenyl, naphthyl, biphenyl, binaphthyl andpyridyl. 5.The process of claim 1 wherein the —OH protective group isselected from the group consisting of acetyl, benzoyl, benzyl and allyl.6. The phosphane of Formula IV of claim 1 with the proviso that when xand y are 1, Ar¹ is not phenyl, Ar² is not p-phenylene and Z¹ is notacetyl protected glucosyl.
 7. A ruthenium complex of the formulaRuH₂(CO)L₃  V wherein L is a phosphane of claim
 2. 8. A palladiumcomplex of the formula L₂PdX₂  VI wherein L is a phosphane of claim 2and X is chlorine or bromine or idomine or acetate.
 9. A palladiumcomplex of the formula L_(z)Pd  VII wherein L is a phosphane of claim 2and z is 3 or
 4. 10. In a hydroformylation of an olefin, the improvementconsisting of performing the hydroformylation in the presence of acatalyst selected from the group consisting of a catalyst of claims 7, 8and
 9. 11. In effecting a Heck reaction, the improvement consisting ofperforming the reaction in the presence of a catalyst selected from thegroup consisting of catalysts of claims 7, 8 and
 9. 12. In effecting aSuzuki reaction, the improvement consisting of performing the reactionin the presence of a catalyst selected from the group consisting ofcatalysts of claims 7, 8 and
 9. 13. In a hydroformylation of an olefin,the improvement consisting of performing the hydroformylation in thepresence of a catalyst comprising rhodium and a phosphane of claim 2.